Azo dyestuffs



Patented Nov. 1, 1938 UNITED STATES PATENT OFFICE AZO DYESTUFFS Detlef Dell's,

Leverkusen,

Helmut Kleiner,

Cologne-Muhlheim, and Theodor Kollmami, Leverlmsen, Germany, assignors to General Aniline Works, Inc., New York, N. Y.,' a corporation of Delaware No Drawing. Application September 16, 1936,

Serial No. 101,078. 1935 20 Claims.

The present invention relates to water insoluble azodyestuifs and to printing preparations suitable for the manufacture of the said dyestuffs by a printing process, more particularly our inven- 6 tion relates to water-insoluble azodyestufis which may be represented by the general formula:

RN=N-R'N=NR" X-Me-O In the said formula R. stands for an aromatic radical which may bear further azo groups, for

example for the radical of the benzene series, of the naphthalene series, of the diphenyl series and the like, R stands for a radical of the benzeneacid group and the carboxylic acid group, are excluded as substituents.

The process of manufacture of the dyestuffs according to the invention is by coupling, especially on the fiber, metal complex compounds of v the azodyestuffs from resorcinol or its homologues, capable of coupling twice, and ortho-hy-' droxyor ortho-carboxydiazo compounds, the 9.20- dyestuffs containing no further solubilizing groups, with diazo compounds suitable for-the manufacture of ice colors. The process may be effected in the manner generally used in the manufacture of ice colors by impregnating the fiber with the azodyestuffs containing metal referred to above and further developing the dyeing with suitable diazo compounds.

A particular method of effecting the process is by bringing the said coupling component on the fiber together with an arylnitrosamine suitable for the manufacture of ice colors (compare U. S. Patent 1,915,734) or a suitable aryldiazo-aminoor -imino-compound soluble in water or an alkaline medium, as obtainable by the condensation 50 of diazo compounds with primary aliphatic or ducing solubility in water, such as the sulfonic In Germany October 28,

aromatic, secondary alphatic, aromatic or heterocyclic bases or cyanamide or cyanamide carboxylic acid (compare U. S. Patents 1,858,623; 1,874,524; 1,867,088; 1,871,850; 1,879,424; 1,882,- 560; 1,882,562; 1,979,327; 1,982,681), and by developing the dyestufi in the customary manner,

e. g. by hanging, steaming or treating with dilute acids or steam containing an acid. (Compare U. S. Patents 1,880,522; 1,882,556; 1,893,991; 2,035,518). In this manner in general brown shades of good fastness properties are obtained.

According to a further feature of the invention for producing the new waterinsoluble azodyestufis by a printing process preparations consisting of the above-named azodyestufls and arylnitrosamines or aryldiazoamino--or -imino-compounds, soluble in water or an alkaline medium, have proved particularly suited. (Compare U. S. Patents 1,882,561; 1,915,734).

The invention is illustrated by the following examples:

Example 1 A cotton tissue is printed with a printing color, containing in 1000 grams:

28 grams of the diazoimino compound from diazotized 4-chloro-2-anisidine and sarcosine,

35 grams of the copper complex compound of the monoazodyestufi from 4-chloro-2-diazophenol and resorcinol,

30 grams of aqueous caustic soda lye 38 B.,

50 grams of glycolmonoethylether,

500 grams of a neutral starch tragacanth thickener, the remainder being water;

then the cotton is dried, steamed for five minutes,

in steam containing acetic acid and/or formic acid, rinsed, boiled, again rinsed and dried. A

full dark brown is obtained.

The dyestuff corresponds to the following formula: V

OCH:

Example 2 l A cotton tissue is printed with a printing color containing in 1000 grams:

43.6 grams of the diazoimino compound from diazotized 4-benzoylamino 2.5-d1methoxy-1- aminobenzene and n-butylamino-acetic acid,

grams of the copper complex compound of the monoazodyestuff from 4-chloro-2-diazothen the cotton is dried, steamed for flve minutes in steam containing acetic acid and/or formic acid, rinsed, soaped, again rinsed and dried. A full blackish brown is thus obtained.

The dyestufi. corresponds to the following formula:

N=N NH.CO.C0H|

0-0u0 Example 3 5.4 grams of the sodiumsalt of the copper complex of the monoazodyestuff prepared from 4-chloro-2-diazophenol and resorcinol are disbCH.

solved in 10 ccm. of aqueous soda lye 38 B.

and 10 ccm. of Turkey red oil, and diluted up to one liter with hot water. In this bath there are treated grams of cotton yarn for half an hour at 30 C. The squeezed yarn is then introduced for half an hour into a developing bath of 10-15 prepared in the usual manner from 2.89 grams of aminoazotoluol by diazotizing, neutralizing the mineral acid with sodium acetate and filling up with water to 1 liter; 'then the yarn is rinsed and soaped in a boiling bath. A full reddish brown is thus obtained.

u'lihe dyestuff corresponds to the following form a:

Grew on m m I O-Cu-O Eeample 4 A cotton tissue is printed with a printing color, containing in 1000 grams:

82.6 grams of the copper complex compound of the monoazodyestufl from 4-chloro-2-diazophenol and resorcinol,

35 grams of the nitrosamine from 4-chloro-2- anisidine (containing 52.2% base),

'50 grams of glycolmonoethylether,

30 grams of aqueous caustic soda lye 38 34%.,

50 grams of' a. neutralchromate solution and 500 grams of a neutral starch tragacanth thickener, the remainder being water;

Example 5 I If nitrosamine Iran s-chloro-a-anisidinei 2 -a,1ss,4sa

as described in Example 4, is substituted by 35.7 grams of the diazoimino compound from diazotized 4-chloro-2-anisidine and piperidine-3-sodium sulfonate, or 50.5 grams of the diazoimino compound from diazotized 1-amino-4-benzoylamino-2.5-diethoxybenzene and methyl-glucamine, or 37.7 grams of the diazoamino compound from diazotized 1-amino-2.5-dimethoxy- 4'-nitro-azobenzene and cyanamidsodium, there i are likewise obtained after treatment with steam containing vapours of acetic acid and/or formic acid full dark brown prints.

Example 6 A cotton tissue is printed with a printing color, containing in 1000 grams:

500 grams of a neutral starch tragacanth thickener, the remainder being water;

then the cotton is dried, treated for 5 minutes with steam containing vapours of acetic and/or formic acid and finished in the usual manner. A full brown print is thus obtained somewhat more yellowish than the analogous print with the dyestuff from resorcinol.

The dyestufi corresponds to the following formula:

on, A c1 N=NQ-ooNacim ast A O--Cu0 n. I

1 Example 7 With a printing paste containing in 1000' grams:

32 grams of the copper complex compound of the monoazo-dyestufl from anthranilic acid and resoi'cinol,

42.2 grams of the diazoimino compound from diazotized 1 amino-2.5-diethoxy-4-benzoylamino-benzene and sarcosine sodium,

50 grams of glycolmonoethylether,

20 grams of aqueous caustic soda lye 38 36.,

500 grams of neutral starch tragacanth thickener,

the remainder being water,

cotton tissue is printed. dried, treated for 5 minutes with steam or steam containing vapours of acetic and/or formic acid and finished in the usual manner. There is obtained a full dark brown with good fastness properties.

mula:

o-oini N=N I QHQ In the following table there are given W combinations prepared in accordance with the invention.

The dyestufl corresponds to the following for- NH- O O- COHI Coupling component I Diazotl nation component Shade Cu-O 0cm N=N OH NH: Roddish brown.

1 0iN(C:H5)g

D NH, Yellowlsh brown.

Dn NH; Reddilh brown.

CHI

D C 'EhC 0 NE NH, subdued brown.

N=N-OOH clmc ONHQNEH Dark blackish brown. 1 C111:

Dn CQHICONH NH! D0.

O CH:

1 D mmconn NH, Full reddish brown.

01 m 0.11.0 ONHQNH; Do.

OCH:

1) NH, Yellov sh brown.

OaN(Ca D NH, Do.

I 0-M n-O 0 0H,

N=N 0H -c.mooNH NH. Rich subdued brown.

01 1) 0.11.0 ONHQNH, Do.

0--Co-O 4 0 0m Q '=N-0H 001.com; NH, Full dark brown.

Dn NH, Reddlsh brown.

s O|N(O:H:)|

Coupling component Diuoflmtlon component Shade .O-Oo-O =N C -on mam blown.

DA N'HI D0- 0-011-0 OCH; I

MG NE, W]: m. M. NO! I I I C!Hl NH: I Do.

D0 mmoonn NH: 'mwmh brown.

Qu--Q 001E! -on CIEICONH m1: Do.

a. n v 05H:

1 O.H|OONH NH; Vloloflsh brown.

m m1. Reddish brown.

OCH;

1). n NH: D0.

m NH: Yellowish brown.

Cn- 0H;

N=N E W21. a'mmwa W m 0 V 7 the first coupling oomponont indicated abova. l

m NH| 7 1. Water insoluble azodyestufl's of the general 7 stands for a radical of the benzene series capable Couplin: component Diuotiution component Shade 0-Ou- 0 0011' s s N=N 0H NH' Shades similar 30 those which are obtained with the first coupling com- 10 I ponent indicated above. 10

O-Gnon com N=N on @101, Vioiotisb brown. 15

OHN=N 0.11.0 ONH NH, Bluish black.

1 NH, Blackisb brown.

'Dn QNH, Deep brown.

D0 m1, Do. 85

0Cu--O 00in; 4&0 .40

N=N N=N OH 0.3.0 ONH NH. Violetiab blackish brown.

0mm H. 01B;

D NE; subdued dark brown.

OOH: 50

m NH, Dark brown.

O-Cu0 00m N=NOOH NB, mum lrown. 55

m NH, Do. 60

'Dn CaHCONHQNH; Blaekish brown I 65 We claim: oi. coupling twice, which is substituted in a position meta to O by a hydroxy group, R" stands for the radical of a diazotized aromatic amine generally used in the manufacture of ice colors, X stands for a member selected from the group consisting of an oxygen atom and the group COO, Me stands for a metallic atom capable or yielding 7 azodyestuff complex compounds, and wherein the bridge XMe is attached to the nuclei in positions ortho to the azo bridge, yielding when produced on the fiber in general brown shades of good fastness properties.

2. Water insoluble azodyestuifs of the general formula:

wherein R and R" stand for benzene radicals, and wherein the bridge OCu--O is attached to the nuclei in positions ortho to the azo bridge, yielding when produced on the fiber in general jr qwn shades of good fastness properties.

ifwa'terinsoluble azodyestuifs of the general formula:

- x N=NR" wherein x stands for a member selected from the group consisting of hydrogen, halogen, the nitro group and an alkyl group, R stands for a radical of the benzene series, yielding when produced on the fiber in general brown shades of good fastness properties.

5. Water insoluble azodyestuffs of the general formula:

alkoxy wherein X stands for a member selected from the group consisting of hydrogen, halogen, the nitro group and an alkyl group, Y stands for a member selected from the group consisting of hydrogen, halogen, alkoxy and alk yl, yielding when produced on the fiber in general brown shades of good fastness properties. 4

6. The water insoluble azodyestufl of the formuia:

yieldingwhenproducedonthefiberafulldark '1. Water insoluble azodyestuffs of the general formula:

I alk'oxy wherein X stands for a member selected from the group consisting of hydrogen, halogen, the nitro group and an alkyl group, Y stands for a member selected from the group consisting of alkoxy and alkyl, yielding when produced on the fiber in general brown shades of good fastness properties.

8. The water insoluble azodyestufl of the formula:

OCH:

=N OH OH:

yielding when produced on the fiber a full blackish brown.

9. Fibers dyed with a dyestuff as claim 1.

10. Fibers dyed with a dyestufl as claimed in claim 2.

11. Fibers dyed with a dyestuif as claimed in claim 3.

12. Fibers dyed with a' dyestufi' as claimed in claim 4.

13. Fibers dyed with a dyestuff as claimed in claim 5.

14. Fibers dyed with a dyestufi as claimed in claim 6.

15. Fibers dyed with a dyestufl as claimed in claim '1.

16. Fibers dyed with a dyestuif as claimed in claim 8.

1'1. Printing preparations comprising a dye-' stuff of the following formula:

xM6,-'O

wherein R. stands for an aromatic radical, R stands for a radical of the benzene series capable of coupling twice, which is substituted in a position meta to 0 by a hydroxy group, X stands for a member selected from the group consisting of an oxygen atom and the group 000, Me standsfor a metallic atom capable of yielding azodyestuff complex compounds, and wherein the bridge XMe-0 is attached to the nuclei in positions ortho to the azo bridge, and a compound selected from the group consisting of nitrosamines, diazoaminoanddiazo-imino compounds derived from aromatic amines generally used in the manufacture of ice colors.

18. Printing preparations comprising a dyestuif of the following formula:

consisting of nitrosamines, diqo-amincand diclaimed in 1 azo-imino compounds derived from aromatic amines generally used in the manufacture of ice colors.

19. Printing preparations comprising a compound of the general formula:

Gr m/OOH wherein X stands for a member selected from the group consisting of hydrogen, halogen, the nitro HzN wherein Y stands for a member selected from the group consisting of hydrogen, halogen, alkoxy and alkyl.

20. Printing preparations comprising a compound of the general formula:

0-0uwherein X stands for a member selected from the group consisting of hydrogen, halogen, the nitro group and an alkyl group, and a compound selected from the group consisting of nitrosamines, diazo-aminoand diazo-imino compounds derived from'an amine of the following general formula:

HaN

group consisting of alkoiw and alkyl.

DETLEF DELFS. HELMUT KLEINER. THEODOR KOLLMANN. 

